CN101469126A - Copolymerization nylon composition and preparation thereof - Google Patents
Copolymerization nylon composition and preparation thereof Download PDFInfo
- Publication number
- CN101469126A CN101469126A CNA2007101728641A CN200710172864A CN101469126A CN 101469126 A CN101469126 A CN 101469126A CN A2007101728641 A CNA2007101728641 A CN A2007101728641A CN 200710172864 A CN200710172864 A CN 200710172864A CN 101469126 A CN101469126 A CN 101469126A
- Authority
- CN
- China
- Prior art keywords
- nylon
- lactan
- copolymerization
- filler
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Polyamides (AREA)
Abstract
The invention relates to a copolymeric nylon composition and a method for preparing the same. In the composition, 1 to 100 weight portions of nylon and 0 to 100 weight portions of filler are dissolved in 100 weight portions of lactam to obtain a mixture of the nylon, the filler and the lactam; and the mixture is added with 0.01 to 10 weight portions of anion polymerization initiator and 0.01 to 50 weight portions of activating agent and has polymerization reaction for 5 to 120 minutes at a temperature of between 100 and 250 DEG C to generate the copolymeric nylon. Compared with the prior art, the method has the characteristics of low reaction temperature, simple equipment requirement and the like.
Description
Technical field
The present invention relates to macromolecular material and preparation method thereof, relate to anionoid polymerization copolymer nylon based on lactan and preparation method thereof particularly.
Background technology
Nylon is one of plastics of consumption maximum, is widely used in fiber, film and various injection, extruded product.Yet homopolymerization nylon often uses because performance is single and is restricted.Copolymerization is one of modified nylon means commonly used.By structure design, it is low to produce fusing point, the material of solubleness height, transparent and various microtextures.
Copolymer nylon is the same with homopolymerization nylon, adopts hydrolytic polymerization more.Usually the preparation copolymer nylon adopts the amine of lactan and hydrolysate and polyfunctionality and acid to prepare through hydrolytic polymerization.But need high pressure, high temperature (250 ℃) and long-time (more than 10～20h) during hydrolytic-polymeric reaction, polymerization unit is comparatively complicated.The molecular weight of hydrolytic polymerization copolymer nylon is subjected to condition restriction, generally can be very not high.And hydrolytic polymerization nylon could the secondary processing moulding after need passing through granulation, extraction, drying.Forming method adopts injection usually.Injection moulding machine will bear very big pressure, the mould complexity, and the requirement on machining accuracy height, production cost is big.
In sum, this area lacks the technology of the very big copolymer nylon of a kind of quick preparation structural adjustment scope.Therefore, this area presses for that exploitation is a kind of to have the high technology of speed of reaction prepare the copolymer nylon that chemical structure can design in wide range.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of temperature of reaction low for the defective that overcomes above-mentioned prior art existence, simple copolymerization nylon composition of equipment requirements and preparation method thereof.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of copolymerization nylon composition is characterized in that, said composition comprises following composition and content (weight part): lactan 100;
Nylon 1-100;
Filler 0-100;
Anionic polymerization initiator 0.01-10;
Activator 0.01-50.
Described lactan is selected from lactan or its combination of C4～12 lactan, bicyclic lactam, replacement; The molecular weight of described nylon is 10000～100000, comprises nylon homopolymer or nylon copolymer; Lactan is different with the acid amides repeating unit of nylon; Described filler comprises mineral filler or polymer packing; Initiator is selected from one or more in basic metal, alkalimetal oxide, alkalimetal hydride, alkali metal hydroxide, the basic metal organic compound; Described activator comprises acyl chlorides, acid anhydrides, isocyanic ester or contains the polymer or the oligopolymer of acyl chlorides, acid anhydrides, isocyanate groups.
The molecular weight of described nylon is 20000～500000, is selected from nylon 6, nylon 66, nylon 1212, NYLON610, nylon 1010, NYLON610 or its combination; Described mineral filler is selected from one or more in carbon black, lime carbonate, quartz, diatomite, ferric oxide, titanium dioxide, zinc oxide, polynite or the glass fibre; Described polymer packing comprises polystyrene, polyethylene oxide, polyoxymethylene, polyvinylpyrrolidone, polyphenylene oxide, polyketone.
A kind of preparation method of copolymerization nylon composition, it is characterized in that, the filler of the nylon of 1-100 weight part and 0-100 weight part is dissolved in the mixture that obtains nylon, filler and lactan in the lactan of 100 weight parts, in this mixture, add the anionic polymerization initiator of 0.01-10 weight part and the activator of 0.01-50 weight part, under 100～250 ℃, carry out polyreaction 5～120min and obtain copolymer nylon.
The reaction pressure of described polyreaction is the normal pressure of static casting; And/or adopt that reaction is extruded, the standard atmosphere pressure of reaction injection moulding, rotational moulding, centrifugal casting moulding and VA RTM technology.
Described copolymer nylon carries out once shaped.
Described one-step moulding method comprises that static casting, reaction are extruded, reaction injection, RTM, rotational moulding or rotational casting.
Described lactan is selected from lactan or its combination of C4～12 lactan, bicyclic lactam, replacement; The molecular weight of described nylon is 10000～100000, comprises nylon homopolymer or nylon copolymer; Lactan is different with the acid amides repeating unit of nylon; Described filler comprises mineral filler or polymer packing; Initiator is selected from one or more in basic metal, alkalimetal oxide, alkalimetal hydride, alkali metal hydroxide, the basic metal organic compound; Described activator comprises acyl chlorides, acid anhydrides, isocyanic ester or contains the polymer or the oligopolymer of acyl chlorides, acid anhydrides, isocyanate groups.
It is 20000～500000 that described nylon selects molecular weight, is selected from nylon 6, nylon 66, nylon 1212, NYLON610, nylon 1010, NYLON610 or its combination; Described mineral filler is selected from one or more in carbon black, lime carbonate, quartz, diatomite, ferric oxide, titanium dioxide, zinc oxide, polynite or the glass fibre; Described polymer packing comprises polystyrene, polyethylene oxide, polyoxymethylene, polyvinylpyrrolidone, polyphenylene oxide, polyketone.
The present invention is dissolved in the nylon of various structures in the lactan by improving preparation technology, causes the anionic ring-opening polymerization of lactan afterwards, utilizes various forming methods to prepare multipolymer between nylon.By other nylon of dissolving different structure, the performance that can in a big way, regulate goods.This process synthesis the improvement of the process advantage of anionic polymerization of lactam and polymer copolymerization to performance.Thereby obtained a kind of novel method for preparing copolymer nylon.The present invention utilizes the low viscosity of lactan melt and high-solvency, the nylon of other structures is dissolved in wherein, and causes quick anionoid polymerization, generates copolymer nylon in the short period of time, has shortened polymerization time greatly.And this method compares with the hydrolytic polymerization method, characteristics such as it is low to have temperature of reaction, and equipment requirements is simple.
Prepare instrument nylon with hydrolytic polymerization and compare, this polymerization process has fast, the polymericular weight advantages of higher of anionic polymerization of lactam speed of reaction.And by in dissolving different structure nylon and the lactan melt, can prepare intensity and modulus and significantly improve (the nylon that contains a nylon of benzene structure such as nylon 6I or side chain, as 3Me6T), the perhaps nylon copolymer (nylon 66, long carbon chain nylons such as nylon 1212) that obviously increases of elongation at break.In addition, by the structure choice of interpolation nylon molecule, can regulate and control the crystal formation (the benzene structure can make the alpha-crystal form of poly-lactam change the γ crystal formation between introducing) and spherulite size (introducing can cause the spherulite size of poly-lactam significantly to reduce to the benzene structure) of nylon copolymer.
Compared with prior art, advantage of the present invention is:
(1) reaction has that speed of response is fast, polymerization temperature is low, polymerization time is short based on the anionic ring-opening polymerization of lactan, equipment simply, characteristics such as monomer conversion height.
(2) can once shaped, simple and convenient processing method.
(3) this process have anionic polymerization of lactam speed of reaction height, monomer conversion height, polymerization temperature is low, molecular weight is big and polymerization and moulding such as can carry out simultaneously at characteristics.Can adopt that rotational moulding, centrifugal casting moulding, reaction are extruded, reaction injection (RIM), reaction injection pultrusion with technologies such as RTM (comprising VA RTM) preparation fibre reinforced composites at polymeric moulded products simultaneously.Prepare copolymer nylon with several anionic polymerization of lactam and compare, this method can be introduced the nylon segment that monomer can't carry out anionic ring-opening polymerization in the copolymer nylon molecule.
Description of drawings
The NMR collection of illustrative plates of the polymkeric substance of Fig. 1 embodiment of the invention 1;
The XRD figure spectrum of Fig. 2 embodiment of the invention 3;
The WAXD collection of illustrative plates of the PA6/MXD6 of Fig. 3 embodiment of the invention 4;
The POM collection of illustrative plates of Fig. 4 embodiment of the invention 5.
Embodiment
Copolymerization nylon composition involved in the present invention and preparation method thereof is described below in conjunction with specific embodiment.
Copolymerization nylon composition its component by weight is as follows:
(A) one or several lactan are 100 parts,
(B) nylon 1-100 part of other structures,
(C) other mineral fillers or polymer packing 0-100 part
(D) initiator 0.01-10 part,
(E) activator 0.01-50 part,
Described lactan comprises that four lactan are to laurolactam and derivative thereof.
" polymer packing " is meant among the present invention, with copolymer nylon of the present invention not the inert polymer of react with as filler.For example, described filler is selected from polystyrene, polyethylene oxide, polyoxymethylene, polyvinylpyrrolidone, polyphenylene oxide, polyketone or its combination.
Component (B) " nylon of other structure " is meant, contains the homopolymer or the multipolymer of acid amides repeating unit on the molecular backbone chain, and its acid amides repeating unit is different from the acid amides repeating unit of component (A) lactan.Promptly, as long as the nylon copolymer that component (A) lactan and component (B) " nylon of other structure " obtain is not a homopolymer yet.
" bicyclic lactam " is meant
" lactan of replacement " is meant the derivative of lactan, also is
Below the technical scheme of composition of the present invention is described in detail:
One or more lactan of component (A)
Adopt lactan as anionic polymerizable monomer in the composition of the present invention.Lactan of the present invention is not particularly limited, and comprises that all can carry out the nylon monomer or the monomer mixture of anionoid polymerization.Particularly, lactan of the present invention comprises the lactan and the bicyclic lactam of 4 to 12 carbon, and other can carry out the nylon monomer or the monomer mixture of anionoid polymerization.
Comprise in the implication of lactan of the present invention and replacing and unsubstituted lactan.In the lactan that replaces, substituting group and the position of substitution do not have particular restriction, only otherwise anionoid polymerization of the present invention is produced restriction to get final product.
Lactan of the present invention can be a kind of lactam monomers, also can be the mixing of multiple lactam monomers.
The consumption of one or more lactan of the present invention is 100 weight parts (this moment, the nylon of other structures was the 1-100 weight part).In a specific embodiment of the present invention, the content of described lactan accounts for the 27.8wt%～99wt% of composition.
The nylon of other structures of component (B)
The nylon of other structures of component of the present invention (B) is homopolymer or the multipolymer that contains the acid amides repeating unit on the molecular backbone chain, and component (A) lactan is different with the acid amides repeating unit of the nylon of other structures of component (B).
Particularly, the nylon of other structures of the present invention comprises nylon 6, nylon 66, and nylon 1212, copolymer nylon (other structure nylon copolymer) waits the homopolymer or the multipolymer that contain the acid amides repeating unit on all molecular backbone chains.The object lesson of homopolymer includes but not limited to: nylon 6, nylon 66, NYLON610, nylon 612, Ni Long11, nylon 12, nylon 1010, Ni Long11 11 and nylon 1212 etc.The object lesson of multipolymer includes but not limited to: nylon 6T/66, nylon 6T/6, nylon 6T/1010, nylon 6T/1212, nylon 6T/612, nylon 6T/610, nylon 6I/66, nylon 6I/6, nylon 6I/1010, nylon 6I/1212, nylon 6I/612 and nylon 9 T etc.
Copolymerization ratio is not particularly limited in the multipolymer, as long as have consistency with lactam monomers of the present invention, is 20/80～80/20 by weight in feed stage for example particularly.
The consumption of the nylon of (B) of the present invention other structures can be the 1-100 weight part, (this moment, the consumption of lactan was 100 weight parts).In a specific embodiment of the present invention, the content of the nylon of described other structures accounts for the 1wt%～50wt% of composition.
The molecular weight or the molecular weight distribution of the nylon of other structures of the present invention are not specifically limited, as long as have consistency with lactam monomers.Having consistency with lactam monomers can be determined by simple and limited test by those skilled in the art.For example, the molecular weight of the nylon of other structures of the present invention is preferably 10000～100000.More preferably 20000～50000.
The nylon (homopolymer or multipolymer) that utilization of the present invention has other structure of certain polymerization degree is dissolved in the lactam monomers, in the anionoid polymerization process, carries out the end group permutoid reaction, and causes quick anionoid polymerization, thereby obtain copolymer nylon fast.
Component (C) mineral filler or polymer packing
Can adopt filler among the present invention, described filler can be one or more mineral fillers or polymer packing.Mineral filler of the present invention or polymer packing are not particularly limited, only otherwise goal of the invention of the present invention is produced restriction to get final product.
Mineral filler for example can be the filler of enhancement type particularly, also can be the increment filler.Preferably, described mineral filler is selected from carbon black, lime carbonate, quartz, diatomite, ferric oxide, titanium dioxide, zinc oxide, polynite or its combination; And/or glass fibre.The preferred thermal silica of described carbon black, precipitated silica.The preferred finely disseminated lime carbonate of described lime carbonate.The preferred finely disseminated quartz of described quartz.
Preferably, polymer packing of the present invention is selected from polystyrene, polyethylene oxide, polyoxymethylene, polyvinylpyrrolidone, polyphenylene oxide, polyketone or its combination.
The consumption of component of the present invention (C) mineral filler or polymer packing can be the 0-100 weight part, (this moment, the consumption of lactan was 100 weight parts).
Component (D) anionic polymerization initiator
The used anionic initiator of the present invention is not particularly limited, as long as belong to the anionic compound of lactan or can generate the anionic compound of lactan with the lactan reaction.Comprise basic metal and oxide compound thereof, hydride and alkali metal hydroxide, basic metal organic compound particularly.The object lesson of basic metal organic compound is including, but not limited to sodium methylate, sodium ethylate.
The consumption of anionic polymerization initiator of the present invention is 0.01-10 weight parts (this moment, the consumption of lactan was 100 weight parts).Preferred 0.1-2 weight part.
Component (E) activator
Activator of the present invention is meant all N-acyl lactams or can is the chemical substance of lactan acidylate, includes, but are not limited to acyl chlorides, acid anhydrides, isocyanic ester, and the polymer or the oligopolymer that contain these chemical groups.
The consumption of the activator of component of the present invention (E) is the 0.01-50 weight part, (this moment, the consumption of lactan was 100 weight parts).
The activator of described component (E) is selected from acyl chlorides, acid anhydrides, isocyanic ester or contains the polymer of these chemical groups or oligopolymer (for example the various superpolymer of maleic anhydride graft, the various superpolymer of TDI grafted).
Below copolymer nylon of the present invention is described in detail:
Copolymer nylon
Copolymer nylon of the present invention synthetic has speed of reaction height, monomer conversion height, polymerization temperature is low, molecular weight is big and polymerization and moulding such as can carry out simultaneously at characteristics.Can adopt that rotational moulding, centrifugal casting moulding, reaction are extruded, reaction injection (RIM), reaction injection pultrusion with technologies such as RTM (comprising VA RTM) preparation fibre reinforced composites at polymeric moulded products simultaneously.Prepare copolymer nylon with several anionic polymerization of lactam and compare, this method can be introduced the nylon segment that monomer can't carry out anionic ring-opening polymerization in the copolymer nylon molecule.
Below preparation method of the present invention is described in detail:
The preparation method
A kind of method for preparing copolymer nylon comprises the steps:
(a) provide the mixture of following component:
One or more lactan 100 weight parts of component (A), the nylon 1-100 weight part of other structures of component (B), component (C) mineral filler or polymer packing 0-100 weight part, component (D) anionic polymerization initiator 0.01-10 weight part, component (E) activator 0.01-50 weight part;
The nylon of other structures of wherein said component (B) is homopolymer or the multipolymer that contains the acid amides repeating unit on the molecular backbone chain, and the nylon of other structures of component (A) is different with the acid amides repeating unit of component (B) lactan;
(b) reaction of the polymerization of mixtures of step (a) obtains copolymer nylon.
Preferably, the order by merging of mixture is as follows described in the step (a):
(i) component (B) and component (C) are dissolved in the component (A), obtain the mixture of component (A), (B), (C);
(ii) add component (D) and component (E) in the mixture that step (i) is obtained, obtain the mixture of step (a).
The condition of polyreaction of the present invention is not specifically limited, only otherwise anionoid polymerization process of the present invention is produced restriction to get final product.Particularly for example:
Reaction pressure in the step (a) is the normal pressure of static casting; And/or adopt that reaction is extruded, the standard atmosphere pressure of technologies such as reaction injection moulding, rotational moulding, centrifugal casting moulding and VA RTM
Temperature of reaction in the step (b) is 100～250; And/or
Reaction times in the step (c) is 5～120min.
In addition, because the present invention's employing is anionic polymerisation, obviously it will be understood by those skilled in the art that and to take the various measures that help anionoid polymerization or do not influence anionoid polymerization.For example, comprise with reactant keep dry, be reflected at carry out under the inert atmosphere and/or reaction process in reduce pressure and dewater, above-mentioned measure all is favourable.
Particularly for example:
1) nylon of other structures is dry under suitable temperature;
2) one or several drying is good nylon are dissolved in the exsiccant lactan melt under vacuum or rare gas element (can be nitrogen, helium etc.) protection;
3) as required other fillers or polymer packing are also dissolved or be dispersed in the lactan melt;
4) add the initiator of lactan, dewater if having water to generate then reduce pressure;
5) add activator
6) utilize the operable working method polymerizations of lactan such as static casting, reaction are extruded, reaction injection, RTM, rotational moulding, rotational casting.
Preferably, preparation method of the present invention also comprises the steps:
(c) copolymer nylon that obtains of described step (b) carries out once shaped.
Preferably, described one-step moulding method be selected from that static casting, reaction are extruded, reaction injection, RTM (ResinTransfer Molding), rotational moulding or rotational casting.
Below in conjunction with specific embodiment, further illustrate the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example usually according to normal condition, for example is " condition in the smooth organic chemistry handbook of Bel Si (Chemical Industry Press, 1996), or the condition of advising according to manufacturer.Ratio and per-cent are based on weight, unless stated otherwise.
1, can access the embodiment (can have a plurality of) of the prescription of better properties, the performance that needs to write exactly this prescription simultaneously is the progressive place of other prescription relatively; 2, adopt the embodiment (can have a plurality of) of the method changed crystal formation to need to write exactly the progressive place of the performance of the material that this method obtains simultaneously.
Embodiment 1
With nylon 1212 (M η=20000) 25g 80 ℃ of dryings 12 hours.100g places there-necked flask hexanolactam, heating and melting, and decompression dewaters.Nylon 1212 is added in the hexanolactam melt, and nitrogen protection is dissolving down.Add sodium hydroxide 0.18g (in the sodium hydroxide solution gross weight), decompression dewaters, and keeps solution at 180 ℃.The TDI (tolylene diisocyanate) that pours 0.4ml then into mixes, and pours in 180 ℃ of moulds, and polymerization is taken out after 20 minutes and promptly got goods.
The NMR collection of illustrative plates of the polymkeric substance of producing as shown in Figure 1.If between nylon 6 and the nylon 1212 copolymerization does not take place, then should only show two absorption peaks on the NMR collection of illustrative plates.But the sample of the method preparation that this patent is wished to protect then presents four peaks, shows between two components copolyreaction has taken place.
Nylon 3Me6T (shown in the following molecular formula 1 of chemical structure) 4g, 8g or 12g are distinguished 80 ℃ of dryings 12 hours.100g places there-necked flask hexanolactam, heating and melting, and decompression dewaters.3Me6T is added in the hexanolactam melt, and nitrogen protection is dissolving down.Add solid sodium hydroxide 0.2g, decompression dewaters, and keeps solution at 180 ℃.Pour MDI 0.4ml then into and mix, pour in 180 ℃ of moulds, polymerization is taken out after 20 minutes and is promptly got goods.
The chemical structure of molecular formula 1 3Me6T:
Mechanics Performance Testing shows that the intensity and the modulus of gained multipolymer significantly improve, and be as shown in table 1.
The mechanical property of table 1 PA6/3Me6T multipolymer
Nylon 6IcoT (G21 of Switzerland EMS company) 4g, 8g or 12g are distinguished 80 ℃ of dryings 12 hours.100g places there-necked flask hexanolactam, heating and melting, and decompression dewaters.3Me6T is added in the hexanolactam melt, and nitrogen protection is dissolving down.Add solid sodium hydroxide 0.2g, decompression dewaters, and keeps solution at 180 ℃.Pour MDI 0.4ml then into and mix, pour in 180 ℃ of moulds, polymerization is taken out after 20 minutes and is promptly got goods.
Mechanics Performance Testing shows that the intensity and the modulus of gained multipolymer significantly improve, and be as shown in table 2.
The mechanical property of table 2 PA6/PA6IcoT multipolymer
In addition, the crystal formation analysis revealed, the existence of PA6IcoT molecule interposition benzene causes a large amount of nylon γ crystalline substance (peak of corresponding 22 ° of positions in the XRD figure spectrum) of nylon 6 generations in the multipolymer, as Fig. 2.Then only there is alpha-crystal form (corresponding 20 ° of bimodal with 24 ° of positions in the XRD figure spectrum) in pure nylon 6.
Embodiment 4
Nylon MXD 6 (chemical structure is shown in molecular formula 2) 4g, 8g or 12g are distinguished 80 ℃ of dryings 12 hours.100g places there-necked flask hexanolactam, heating and melting, and decompression dewaters.3Me6T is added in the hexanolactam melt, and nitrogen protection is dissolving down.Add solid sodium hydroxide 0.2g, decompression dewaters, and keeps solution at 180 ℃.Pour MDI 0.4ml then into and mix, pour in 180 ℃ of moulds, polymerization is taken out after 20 minutes and is promptly got goods.
The chemical structure of molecular formula 2MXD6
After crystal formation analysis revealed, MXD6 add since between the existence of benzene structure, cause most of alpha-crystal form of pure nylon 6 to change the γ crystal formation into, as Fig. 3.
Embodiment 5
Nylon 6 is distinguished 80 ℃ of dryings 12 hours with nylon 6T multipolymer (PA6co6T) (molecular weight Mw=25000, copolymerization ratio 1:1) 4g, 8g or 12g.100g places there-necked flask hexanolactam, heating and melting, and decompression dewaters.Nylon 6/6T is added in the hexanolactam melt, and nitrogen protection is dissolving down.Add solid sodium hydroxide 0.2g, decompression dewaters, and keeps solution at 180 ℃.Pour acetylize hexanolactam 0.3g then into and mix, pour in 190 ℃ of moulds, polymerization is taken out after 20 minutes and is promptly got goods.
The mechanical property of resulting product is shown in Table 3.Can find, compare that add after PA6co6T and the nylon 6 generation copolymerization, the intensity of goods, modulus and elongation at break increase simultaneously with pure nylon 6.
The mechanical property of table 3 PA6/PA6co6T multipolymer
In addition, the spherulite size of the multipolymer of PA6co6T and nylon 6 copolymerization gained significantly reduces, as shown in Figure 4.
Embodiment 6
With 20g80 ℃ of drying of nylon 6 (about Mw=10000) 12 hours.Two hexamethylene lactan 100g are placed there-necked flask, heating and melting, dewater (upper limit of reaction pressure) reduces pressure.Nylon 6, carbon black 10g are added in the two hexamethylene lactan melts, and nitrogen protection is dissolving down.Add sodium hydride 0.12g, decompression dewaters, and keeps solution at 180 ℃.Pour acetylize hexanolactam 0.6ml then into and mix, pour in 250 ℃ of moulds, polymerization is taken out after 120 minutes and is promptly got goods.
Embodiment 7
With 80 ℃ of dryings of nylon 1212 (about Mw=100000) 10g 12 hours.100g places there-necked flask laurolactam, heating and melting, and decompression dewaters.Nylon 1212, diatomite 15g are added in the laurolactam melt, and nitrogen protection is dissolving down.Add sodium hydride 0.15g, decompression dewaters, and keeps solution at 180 ℃.Pour MDI 0.4ml then into and mix, pour in 110 ℃ of moulds, polyase 13 takes out after 0 minute and promptly gets goods.
With 80 ℃ of dryings of nylon 1010 (Mw=40000) 16g 12 hours.100g places there-necked flask butyrolactam, heating and melting, and decompression dewaters.Nylon 1010, titanium dioxide 5g are added in the butyrolactam melt, and nitrogen protection is dissolving down.Add sodium hydride 0.15g, decompression dewaters, and keeps solution at 180 ℃.Pour isocyanic ester 0.3ml then into and mix, pour in 190 ℃ of moulds, polymerization is taken out after 20 minutes and is promptly got goods.
Embodiment 9
With nylon 1212 and 80 ℃ of dryings of each 10g of nylon 6I 12 hours.100g places there-necked flask hexanolactam, heating and melting, and decompression dewaters.Nylon 1212 and nylon 6I, ferric oxide 20g are added in the hexanolactam melt, and nitrogen protection is dissolving down.Add NaOH 0.2g, decompression dewaters, and keeps solution at 180 ℃.Pour in 250 ℃ of moulds, polymerization is taken out after 40 minutes and is promptly got goods.
With nylon 6 and 80 ℃ of dryings of nylon 6T multipolymer (nylon 6/6T) (molecular weight Mw=30000) 10g 12 hours.Laurolactam and each 50g of hexanolactam are placed there-necked flask, heating and melting, decompression dewaters.Nylon 6/6T is added in laurolactam and the hexanolactam melt, and nitrogen protection is dissolving down.Add NaOH 0.2g, decompression dewaters, and keeps solution at 180 ℃.Pour TDI 0.35ml then into and mix, pour in 190 ℃ of moulds, polymerization is taken out after 20 minutes and is promptly got goods.
Claims (9)
1. a copolymerization nylon composition is characterized in that, said composition comprises following composition and content (weight part): lactan 100;
Nylon 1-100;
Filler 0-100;
Anionic polymerization initiator 0.01-10;
Activator 0.01-50.
2. a kind of copolymerization nylon composition according to claim 1 is characterized in that, described lactan is selected from lactan or its combination of C4～12 lactan, bicyclic lactam, replacement; The molecular weight of described nylon is 10000～100000, comprises nylon homopolymer or nylon copolymer; Lactan is different with the acid amides repeating unit of nylon; Described filler comprises mineral filler or polymer packing; Initiator is selected from one or more in basic metal, alkalimetal oxide, alkalimetal hydride, alkali metal hydroxide, the basic metal organic compound; Described activator comprises acyl chlorides, acid anhydrides, isocyanic ester or contains the polymer or the oligopolymer of acyl chlorides, acid anhydrides, isocyanate groups.
3. a kind of copolymerization nylon composition according to claim 2 is characterized in that the molecular weight of described nylon is 20000～500000, is selected from nylon 6, nylon 66, nylon 1212, NYLON610, nylon 1010, NYLON610 or its combination; Described mineral filler is selected from one or more in carbon black, lime carbonate, quartz, diatomite, ferric oxide, titanium dioxide, zinc oxide, polynite or the glass fibre; Described polymer packing comprises polystyrene, polyethylene oxide, polyoxymethylene, polyvinylpyrrolidone, polyphenylene oxide, polyketone.
4. the preparation method of a copolymerization nylon composition as claimed in claim 1, it is characterized in that, the filler of the nylon of 1-100 weight part and 0-100 weight part is dissolved in the mixture that obtains nylon, filler and lactan in the lactan of 100 weight parts, in this mixture, add the anionic polymerization initiator of 0.01-10 weight part and the activator of 0.01-50 weight part, under 100～250 ℃, carry out polyreaction 5～120min and obtain copolymer nylon.
5. the preparation method of a kind of copolymerization nylon composition according to claim 4 is characterized in that, the reaction pressure of described polyreaction is the normal pressure of static casting; And/or adopt that reaction is extruded, the standard atmosphere pressure of reaction injection moulding, rotational moulding, centrifugal casting moulding and VA RTM technology.
6. the preparation method of a kind of copolymerization nylon composition according to claim 4 is characterized in that, described copolymer nylon carries out once shaped.
7. the preparation method of a kind of copolymerization nylon composition according to claim 6 is characterized in that, described one-step moulding method comprises that static casting, reaction are extruded, reaction injection, RTM, rotational moulding or rotational casting.
8. the preparation method of a kind of copolymerization nylon composition according to claim 4 is characterized in that, described lactan is selected from lactan or its combination of C4～12 lactan, bicyclic lactam, replacement; The molecular weight of described nylon is 10000～100000, comprises nylon homopolymer or nylon copolymer; Lactan is different with the acid amides repeating unit of nylon; Described filler comprises mineral filler or polymer packing; Initiator is selected from one or more in basic metal, alkalimetal oxide, alkalimetal hydride, alkali metal hydroxide, the basic metal organic compound; Described activator comprises acyl chlorides, acid anhydrides, isocyanic ester or contains the polymer or the oligopolymer of acyl chlorides, acid anhydrides, isocyanate groups.
9. the preparation method of a kind of copolymerization nylon composition according to claim 8, it is characterized in that, it is 20000～500000 that described nylon selects molecular weight, is selected from nylon 6, nylon 66, nylon 1212, NYLON610, nylon 1010, NYLON610 or its combination; Described mineral filler is selected from one or more in carbon black, lime carbonate, quartz, diatomite, ferric oxide, titanium dioxide, zinc oxide, polynite or the glass fibre; Described polymer packing comprises polystyrene, polyethylene oxide, polyoxymethylene, polyvinylpyrrolidone, polyphenylene oxide, polyketone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101728641A CN101469126A (en) | 2007-12-24 | 2007-12-24 | Copolymerization nylon composition and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101728641A CN101469126A (en) | 2007-12-24 | 2007-12-24 | Copolymerization nylon composition and preparation thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101469126A true CN101469126A (en) | 2009-07-01 |
Family
ID=40826939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101728641A Pending CN101469126A (en) | 2007-12-24 | 2007-12-24 | Copolymerization nylon composition and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101469126A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103337325A (en) * | 2012-12-19 | 2013-10-02 | 横店集团东磁股份有限公司 | Nylon ferrite composite magnet device and fabrication method thereof |
| CN104761894A (en) * | 2015-04-22 | 2015-07-08 | 合肥康龄养生科技有限公司 | Nylon composite material with high transparency and glossiness and preparation method of nylon composite material |
| CN104761890A (en) * | 2015-04-22 | 2015-07-08 | 合肥康龄养生科技有限公司 | Cold-resistant and low-temperature-resistant nylon composite material and preparation method thereof |
| CN104774451A (en) * | 2015-04-22 | 2015-07-15 | 合肥康龄养生科技有限公司 | Odorless smellless high-property nylon composite material and preparation method thereof |
| CN105462239A (en) * | 2016-01-05 | 2016-04-06 | 株洲时代新材料科技股份有限公司 | Glass fiber reinforced nylon material for rail and preparation method of glass fiber reinforced nylon material |
| CN106478942A (en) * | 2016-09-30 | 2017-03-08 | 湖南工业大学 | A kind of high obstructing performance rotational moulding nylon products and preparation method thereof |
| CN107142551A (en) * | 2017-06-27 | 2017-09-08 | 江苏科技大学 | A kind of antibacterial superfine polyamide fiber and its reactive extrursion preparation method |
| CN107337794A (en) * | 2017-07-07 | 2017-11-10 | 株洲时代新材料科技股份有限公司 | A kind of copolymer nylon containing hexatomic ring and preparation method thereof |
| CN110951073A (en) * | 2019-12-16 | 2020-04-03 | 山东东辰瑞森新材料科技有限公司 | Copolymerized nylon 612 material |
| CN113527670A (en) * | 2021-08-06 | 2021-10-22 | 东莞市凯泰汽车零部件有限公司 | 1200H xenon lamp aging-resistant urea tube and preparation method thereof |
-
2007
- 2007-12-24 CN CNA2007101728641A patent/CN101469126A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103337325A (en) * | 2012-12-19 | 2013-10-02 | 横店集团东磁股份有限公司 | Nylon ferrite composite magnet device and fabrication method thereof |
| CN104761894A (en) * | 2015-04-22 | 2015-07-08 | 合肥康龄养生科技有限公司 | Nylon composite material with high transparency and glossiness and preparation method of nylon composite material |
| CN104761890A (en) * | 2015-04-22 | 2015-07-08 | 合肥康龄养生科技有限公司 | Cold-resistant and low-temperature-resistant nylon composite material and preparation method thereof |
| CN104774451A (en) * | 2015-04-22 | 2015-07-15 | 合肥康龄养生科技有限公司 | Odorless smellless high-property nylon composite material and preparation method thereof |
| CN105462239A (en) * | 2016-01-05 | 2016-04-06 | 株洲时代新材料科技股份有限公司 | Glass fiber reinforced nylon material for rail and preparation method of glass fiber reinforced nylon material |
| CN105462239B (en) * | 2016-01-05 | 2018-09-07 | 株洲时代新材料科技股份有限公司 | Track glass fiber reinforced nylon material and preparation method thereof |
| CN106478942A (en) * | 2016-09-30 | 2017-03-08 | 湖南工业大学 | A kind of high obstructing performance rotational moulding nylon products and preparation method thereof |
| CN107142551A (en) * | 2017-06-27 | 2017-09-08 | 江苏科技大学 | A kind of antibacterial superfine polyamide fiber and its reactive extrursion preparation method |
| CN107337794A (en) * | 2017-07-07 | 2017-11-10 | 株洲时代新材料科技股份有限公司 | A kind of copolymer nylon containing hexatomic ring and preparation method thereof |
| CN110951073A (en) * | 2019-12-16 | 2020-04-03 | 山东东辰瑞森新材料科技有限公司 | Copolymerized nylon 612 material |
| CN113527670A (en) * | 2021-08-06 | 2021-10-22 | 东莞市凯泰汽车零部件有限公司 | 1200H xenon lamp aging-resistant urea tube and preparation method thereof |
| CN113527670B (en) * | 2021-08-06 | 2023-10-13 | 东莞市凯泰汽车零部件有限公司 | 1200H xenon lamp aging resistant urea pipe and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101469126A (en) | Copolymerization nylon composition and preparation thereof | |
| EP2022809B1 (en) | A method for preparing nylon microsphere and the same | |
| CN106414554B (en) | Method for producing thermoplastic materials made of semi-crystalline polyamide | |
| AU724986B2 (en) | Method for producing, and use of, a catalytically-acting liquid system for anionic lactam polymerization | |
| US20120088899A1 (en) | Process for producing monomer compositions and use of these for producing a polyamide molding | |
| CN102391642A (en) | Preparation method of modified monomer cast (MC) nylon 6 blending material | |
| Rwei et al. | Synthesis and characterization of low melting point PA6 copolyamides from ε-caprolactam with bio-based polyamide salt | |
| CN103172801A (en) | Preparation method of polyurethane/styrene elastomer composite material | |
| CN104428345B (en) | For producing the catalyst of cast polyamides, the method and application thereof for producing the catalyst | |
| EP3383937B1 (en) | Improved polymer preparation | |
| CN104830053A (en) | Caprolactam-laurolactam co-polymer modified by glass fiber and preparation method of powder thereof | |
| US20160068679A1 (en) | Polymerizable lactam composition containing a sulfonated polyaryl sulfone | |
| EP0256323B1 (en) | Improved process for the anionic polymerization of caprolactam, and for the copolymerization thereoff with other lactams | |
| CN101560294B (en) | Compatible thermotropic liquid crystal polymer and method and application thereof | |
| Ahmadi et al. | Novel anionic polymerization of ε-caprolactam towards polyamide 6 containing nanofibrils | |
| CN1978486A (en) | High-toughness nylon alloy, and its preparing method | |
| CN104877130A (en) | Synthetic method of polylactic acid-gamma aminobutyric acid copolymerization material | |
| CN105131279B (en) | A kind of method that reaction extrusion in-situ polymerization prepares SEBS g PA6 | |
| CN112280031B (en) | High-temperature-resistant semi-aromatic polymer and preparation method thereof | |
| KR102041358B1 (en) | Compositions comprising lactam | |
| CN113214470A (en) | Preparation method of low-melting-point polybutyrolactam | |
| CA2796798A1 (en) | Process for the production of pa-410 and pa-410 obtainable by that process | |
| CN105885396A (en) | Natural fibrilia reinforced cast nylon composite material and preparation method thereof | |
| CN115246932B (en) | Compatilizer PS-g-POP and preparation method and application thereof | |
| CN1103408A (en) | Synthesis of random styrene-maleic anhydride copolymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090701 |